Beta-alumina solid electrolyte

ABSTRACT

A beta-alumina solid electrolyte for use in a sodium-sulfur battery is composed of beta-alumina crystals having a degree of orientation toward the C axis thereof, of 0.2-0.4 and an aspect ratio of 4.0 or less. The beta-alumina solid electrolyte is composed of the beta-alumina crystals having a degree of orientation toward the C axis thereof, of 0.2-0.4 and has such a particle diameter distribution that the average particle diameter is 3 μm or less, the proportion of the particles having a particle diameter of 5 μm or less is 90% or more, and the maximum particle diameter is 300 μm or less. A process for producing a beta-alumina solid electrolyte using an alumina source material, a magnesium source material and a sodium source material, uses a magnesium-aluminum spinel as the magnesium source material and subjects all materials to mixing, granulation, molding and firing to obtain a beta-alumina solid electrolyte without subjecting the materials to calcination. The beta-alumina solid electrolyte has a low electrical resistance and a large strength to internal water pressure and exhibits excellent properties when used as a diaphragm for a sodium-sulfur battery.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a beta-alumina solid electrolyte havingexcellent properties such as low electrical resistance, high strengthand the like, as well as to a process for production thereof. Moreparticularly, the present invention relates to a process for productionof beta-alumina solid electrolyte, which can produce a beta-aluminasolid electrolyte of having excellent properties without subjecting thematerials to calcination (calcination is conducted in conventionalprocesses).

2. Prior Art

Beta-Alumina solid electrolytes have a very high sodium ionconductivity, i.e. a low electrical resistance. Hence, attention isbeing paid to their use as a diaphragm for a sodium-sulfur battery, andthe like.

Of the beta-alumina solid electrolytes, a an MgO-stabilized beta-aluminasolid electrolyte has conventionally been produced as follows. That is,the materials, i.e. MgO, a sodium compound and α-Al₂ O₃ are mixed at anappropriate ratio; the mixture is calcined to obtain beta-alumina;grinding is conducted; the ground material is then granulated, moldedinto a desired shape and fired to obtain a beta-alumina solidelectrolyte.

The reason why the materials are calcined beforehand to obtainbeta-alumina, is that when beta-alumina is produced by direct firingwithout conducting calcination, severe volume expansion in the phasetransition from α-Al₂ O₃ to beta-alumina occurs, making it difficult toobtain a beta-alumina solid electrolyte of uniform quality and highstrength.

In the conventional process, however, since the materials are calcinedbeforehand to obtain beta-alumina, the steps become complex and invite ahigh cost. Hence, it is strongly desired in production of asodium-sulfur battery, and the like to shorten the total productionsteps and produce a beta-alumina solid electrolyte more efficiently.

Further, since the above-mentioned conventional process conductspreliminary calcination (to obtain beta-alumina), grinding, granulation,molding and firing, the crystals constituting the resulting beta-aluminasolid electrolyte have high orientation. Moreover, the beta-aluminacontains large crystals because crystal growth takes place while thebeta-alumina formed by calcination is acting as a nucleus for crystalgrowth. In addition, many of the large crystals have a shape of largeaspect ratio, i.e. a thin and long shape.

OBJECT AND SUMMARY OF THE INVENTION

An object of the present invention is to produce a beta-alumina solidelectrolyte efficiently without calcination of the materials. Anotherobject of the present invention is to provide a beta-alumina solidelectrolyte having low electrical resistance and high strength withrespect to internal water pressure.

According to the present invention, there is provided a beta-aluminasolid electrolyte for use in a sodium-sulfur battery, wherein thebeta-alumina crystals constituting said electrolyte have a degree oforientation toward the C axis thereof, of 0.2-0.4 and an aspect ratio of4.0 or less.

According to the present invention, there is also provided abeta-alumina solid electrolyte for use in a sodium-sulfur battery,wherein the beta-alumina crystals constituting said electrolyte have adegree of orientation toward the C axis thereof, of 0.2-0.4 and has havesuch a particle diameter distribution that the average particle diameteris 3 μm or less, the proportion of the particles having a particlediameter of 5 μm or less is 90% or more, and the maximum diameter is 300μm or less.

The beta-alumina solid electrolyte of the present invention preferablyhas an electrical resistance of 4.0 Ω.cm or less, a burst strength tointernal pressure of 150 MPa or more, and a density of 3.20 g/cm³ ormore.

According to the present invention there is further provided a processfor producing a beta-alumina solid electrolyte using an alumina sourcematerial, a magnesium source material and a sodium source material,which comprises using a magnesium-aluminium spinel as the magnesiumsource material and subjecting all materials to mixing, granulation,molding and firing to obtain a beta-alumina solid electrolyte withoutsubjecting the materials to calcination.

In the process of the present invention, it is preferable that the molarratio of magnesia and alumina in the magnesium-aluminum spinel is 1 ormore, and further, that the sodium source material is sodium compound(s)containing at least either NaHCO₃ or sodium oxalate.

In the process of the present invention, it is also preferable forproperty improvement in electrical resistance, strength, and the likethat the firing is conducted according to a heat curve comprising:

(1) a step of keeping the system temperature at a constant temperaturein the range of 1,400°-1,550° C. for 1-5 hours, or a step of increasingthe system temperature at a rate of 50° C./hr or less in saidtemperature range,

(2) a step of keeping the system temperature at the maximum temperatureof 1,580°-1,650° C. for 0.1-3.0 hours, and

(3) a step of keeping the system temperature at a constant temperaturein the range of 1,400°-1,550° C. for 1-5 hours, or a step of decreasingthe system temperature at a rate of 50° C./hr or less in saidtemperature range.

In the present invention, the beta-alumina is a generic name for β-Al₂O₃ (Na₂ O.11Al₂ O₃), β"-Al₂ O₃ (Na₂ O.5Al₂ O₃), β'"-Al₂ O₃, and the likeand refers particularly to a beta-alumina containing β"-Al₂ O₃ in anamount of 95% or more.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view of a single crystal of the beta-alumina solidelectrolyte of the present invention.

FIG. 2 is a perspective view showing a test piece obtained by cuttingthe beta-alumina sintered material of the present invention in thelengthwise direction.

FIG. 3 is a view showing an example of the constitution of the Na/Naconductivity tester for measurement of electrical resistance, used inthe present invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is hereinafter described in detail.

A main feature of the present invention is that in the production of abeta-alumina solid electrolyte, magnesium-aluminum spinel is used as amagnesium source material which is a stabilizer for beta-alumina, inplace of MgO, and the like used in the conventional process. Allmaterials including magnesium-aluminum spinel are mixed; the mixture isgranulated without being calcined, followed by molding and firing;thereby, a beta-alumina having excellent properties when used as a solidelectrolyte can be obtained.

The present inventor made a study from various angles in order toshorten the conventional steps for beta-alumina production. As a result,the present inventor discovered that when magnesium-aluminum spinel isused in place of conventional MgO, as a magnesium source material, thespinel is presumed to act as a seed crystal for beta-alumina crystalformation in the firing step of beta-alumina production and thecalcination of materials for beta-alumina formation becomes unnecessary.

The magnesium-aluminum spinel used as a magnesium source material has amagnesia (MgO)/alumina (Al₂ O₃) molar ratio of preferably 1 or more(MgO-rich), more preferably 1.0-1.5. The reason is not clear but, whenthe molar ratio is outside the above range, the resulting beta-aluminahas slightly inferior properties in electrical resistance, strength, andthe like.

Further, the magnesium-aluminum spinel is preferably fine andspecifically has an average particle diameter of preferably 1 μm orless, more preferably 0.5 μm or less. Furthermore, themagnesium-aluminum spinel preferably has a 90% particle diameter of 10μm or less, preferably 5 μm or less. Moreover, the magnesium-aluminumspinel preferably has a specific surface area of 5 m² /g or more. Whenthe magnesium-aluminum spinel has the particle diameter and specificsurface area in the above ranges, the resulting beta-alumina sinteredmaterial has small crystal orientation and a small crystal aspect ratioand thus has good properties.

As the sodium compound for the sodium source material, there can be usedconventionally known compounds such as Na₂ CO₃ and the like. However,use of sodium hydrogencarbonate (NaHCO₃) or sodium oxalate is preferablebecause segregation of the sodium compound in the granulation productcan be avoided and uniform dispersion can be achieved. That is, NaHCO₃or sodium oxalate, having lower solubility in the solvent used (e.g.water) than Na₂ CO₃, precipitates rapidly during drying for granulationand can be dispersed uniformly in the granulation production. Use ofNaHCO₃ or sodium oxalate is also preferable because, when materialsincluding NaHCO₃ or sodium oxalate are mixed in a slurry state, theslurry can be controlled at a pH of about 10, making it easy to selectan organic binder.

NaHCO₃ or sodium oxalate may be used singly, or may be used as a mixturewith Na₂ CO₃.

The NaHCO₃ or sodium oxalate used has an average particle diameter ofpreferably 5 μm or less.

The alumina source material is preferably α-Al₂ O₃. It is preferablyfine and has an average particle diameter of 1 μm or less, particularlypreferably 0.5 μm or less. The α-Al₂ O₃ also has a specific surface areaof preferably 5 m² /g or more, more preferably 10 m² /g or more. Whenthe α-Al₂ O₃ has a particle diameter in the above range, the resultingbeta-alumina sintered material scarcely contains large crystals andtends to be dense and have a low resistance.

The alumina source material, the magnesium source material and thesodium source material all having desired properties in particlediameter, and the like as mentioned above, are mixed in givenproportions allowing for beta-alumina formation. The mixing is conductedby grinding the materials in water, whereby a slurry is prepared. Mixingas uniform as possible is preferable because it can improvesinterability in the firing step.

The slurry is granulated using a spray dryer or the like. Thisgranulation step is conducted to make the mixing of materials uniformand improve moldability in the subsequent molding step. In thegranulation step, a granulation product is produced so as to generallyhave an average particle diameter of 50-100 μm.

The granulation product is then molded into a desired shape.

The molding is made into a tubular shape in many cases because thebeta-alumina solid electrolyte of the present invention is suitably usedmainly as a diaphragm for a sodium-sulfur battery.

The molding is conducted at a pressure of 1.5 ton/cm² or more,preferably 2.0 ton/cm² or more, whereby a molded material having adensity of 1.9 g/cm³ or more is produced.

Then, the molded material is fired under given conditions, wherebygrowth of uniform crystals is accelerated and beta-alumina crystals areformed. In this case, it is preferable to set the firing conditions andfiring heat curve as described below. In the present invention, sincemagnesium-aluminum spinel is used as a seed crystal for beta-aluminaformation, the volume expansion associated with the phase transitionfrom α-Al₂ O₃ to beta-alumina poses no big problem. However, it ispreferable to appropriately control the heat curve for firing in orderto obtain a beta-alumina solid electrolyte of uniform quality, largestrength and low electrical resistance.

Hence, it is important to set the maximum firing temperature at1,580°-1,650° C. in order to obtain a beta-alumina containing a highproportion of β"-Al₂ O₃ having good properties. Specifically, the heatcurve preferably comprises at least three steps:

(1) a step of keeping the system temperature at a constant temperaturein the range of 1,400°-1,550° C. (in this temperature range, β-Al₂ O₃changes to β"-Al₂ O₃) for 1-5 hours, or a step of increasing the systemtemperature at a rate of 50° C./hr or less in said temperature range,

(2) a step of keeping the system temperature at the maximum temperatureof 1,580°-1,650° C. for 0.1-3.0 hours, and

(3) a step of keeping the system temperature at a constant temperaturein the range of 1,400°-1,550° C. for 1-5 hours, or a step of decreasingthe system temperature at a rate of 50° C./hr or less in saidtemperature range.

The above heat curve is effective because it can increase the β"-Al₂ O₃content in beta-alumina to 95% or more.

The beta-alumina solid electrolyte obtained by the process of thepresent invention has unique inherent characteristics in that thebeta-alumina crystals constituting the solid electrolyte have smallorientation and a small aspect ratio.

Specifically, the beta-alumina crystals constituting the solidelectrolyte have a degree of crystal orientation toward the C axisthereof, of 0.2-0.4, preferably 0.25-0.35 and an aspect ratio of 4.0 orless, preferably 3.0 or less.

Beta-alumina crystals have a hexagonal crystal structure and, in eachsingle crystal as seen in FIG. 1 showing a schematic view ofbeta-alumina solid electrolyte single crystal, have an Na-ion-conductiveplane in the plane formed by the A axis and the B axis, i.e. the A-Bplane, and show no conductivity toward a direction perpendicular to theA-B plane, i.e. the C axis direction. Further, the crystals, having acleaving property along the A-B plane, have low tensile strength in theC axis direction. Hence, the beta-alumina crystals preferably have loworientation. In the conventional process for production of beta-aluminacrystals (said process includes a step of calcination of materials),however, it has been difficult to produce beta-alumina crystals of loworientation.

Incidentally, the degree of crystal orientation toward the C axisthereof, of beta-alumina solid electrolyte which is a polycrystal, wasmeasured as follows.

The beta-alumina sintered material obtained by the given productionprocess was cut to obtain a test piece of 1 mm in width and 40 mm inlength, shown in FIG. 2. The test piece was polished at the outersurface to remove the unevennesses of the surface. The outer surface ofthe polished test piece was subjected to analysis by an X-ray analyzerto obtain the diffraction pattern of the surface, and the relativeamounts of various crystal faces, each directing toward the diameterdirection of a beta-alumina tube, were calculated.

In the specific measurement, an X-ray analyzer of the goniometer typewas used. Using characteristic X-rays, a tube voltage of 35 KV and atube current of 20 mA, a diffraction pattern was recorded on a chart.For various crystal faces each having a given angle (0°, 33.3°, 60° or90°) to the C axis of the beta-alumina crystals, there were measuredrespective peak heights, and the proportion of each crystal face wasexpressed as a relative value. The relative values of beta-aluminacrystal faces are shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________                         Peak Orientation                                         Angle between        height                                                                             degree                                              C axis and                                                                            Crystal                                                                           Diffraction angle                                                                      measured                                                                           of crystal face                                     crystal face (°)                                                               face                                                                              2 θ (°)                                                                   (mm) (relative value)                                    __________________________________________________________________________    0.0     006 15.0˜16.0                                                                        H.sub.1                                                                            H.sub.1 /(H.sub.1 + H.sub.2 + H.sub.3 +                                       H.sub.4)                                            33.3    101 32.0˜32.5                                                                        H.sub.2                                                                            H.sub.2 /(H.sub.1 + H.sub.2 + H.sub.3 +                                       H.sub.4)                                            60.0    104 20.0˜21.0                                                                        H.sub.3                                                                            H.sub.3 /(H.sub.1 + H.sub.2 + H.sub.3 +                                       H.sub.4)                                            90.0    110 31.5˜32.0                                                                        H.sub.4                                                                            H.sub.4 /(H.sub.1 + H.sub.2 + H.sub.3 +             __________________________________________________________________________                              H.sub.4)                                        

In the present invention, "degree of crystal orientation toward C axis"refers to the relative value of the peak height (H₁ of Table 1) (whenthe angle between C axis and crystal face is 0°, that is, the crystalface agrees with the C axis, to total peak height (H₁ +H₂ +H₃ +H₄), i.e.H₁ /(H₁ +H₂ +H₃ +H₄). When the degree of crystal orientation toward Caxis is high, the non-conductive face of the beta-alumina crystals isdirected to the Na-ion-conductive direction of the beta-alumina tubeand, as a result, the beta-alumina tube has a high resistance.

In the present invention, the aspect ratio of beta-alumina crystals ismeasured as follows.

The beta-alumina sintered material is cut to obtain a small test piece.The test piece is polished and etched at a section. The resultingsection is observed using a scanning type electron microscope andphotographed at a magnification allowing for the observation ofindividual particles. Using the photograph, the major axis and minoraxis of each individual particle were measured and the average of theirratios was taken as the aspect ratio of the sintered material.

When the degree of crystal orientation toward C axis, of thebeta-alumina crystals is smaller than 0.2, the crystals have a smallelectrical resistance but small mechanical strength (e.g. small burststrength to internal pressure) and is unsuitable for use as a diaphragmfor a sodium-sulfur battery. When the degree of crystal orientation islarger than 0.4, the crystals have large mechanical strength but anelectrical resistance thereof is too high.

When the aspect ratio of beta-alumina crystals deviates from the aboverange, the beta-alumina crystals are too thin and long, making itimpossible to obtain a beta-alumina solid electrolyte having excellentproperties (e.g. low electrical resistance, high strength, and the like)in good balance.

Further in the present invention, the beta-alumina crystals constitutingthe beta-alumina solid electrolyte have such a particle diameterdistribution that the average particle diameter is 3 μm or less, theproportion of the particles having a particle diameter of 5 μm or lessis 90% or more, and the maximum particle diameter is 300 μm or less,preferably 200 μm or less. In the beta-alumina crystals, the size oflarge crystals present therein is small and their amount is also small.

As described above, the beta-alumina solid electrolyte of the presentinvention has a particular crystal structure and shows excellentproperties when used as a diaphragm for a sodium-sulfur battery.

Specifically, the present beta-alumina solid electrolyte has anelectrical resistance of 4.0 Ω.cm or less, preferably 3.5 Ω.cm or less,a burst strength to internal pressure of 150 MPa or more, preferably 180MPa or more, and a density of 3.20 g/cm³ or more, preferably 3.22 g/cm³or more.

The present invention is hereinafter described in more detail by way ofExamples. However, the present invention is not restricted to theseExamples.

EXAMPLE 1 AND COMPARATIVE EXAMPLE 1

The following three raw materials were weighed: (i) an α-Al₂ O₃ powderhaving an average particle diameter of 1.5 μm and a specific surfacearea of 3.5 m² /g as measured by BET adsorption method, (ii) Na₂ CO₃having an average particle diameter of 1 μm, and (iii) amagnesium-aluminum spinel having an average particle diameter, a 90%particle diameter and a MgO/Al₂ O₃ molar ratio all shown in Table 2, inproportions allowing for beta-alumina formation, i.e. proportions of 71%(Al₂ O₃), 14% (spinel) and 15% (Na₂ CO₃). The raw materials wereuniformly mixed in water using a ball mill to prepare a slurry.

The slurry was granulated into grains having an average particlediameter of 60 μm using a spray dryer. The grains were molded into atubular molded material having a 25 mm diameter, a 230 mm length and a1.3 mm thickness, at a pressure of 2 ton/cm² using an isostatic press.

The molded material was placed in an MgO-made sagger and fired at themaximum temperature of 1,600° C. for 30 minutes to obtain a beta-aluminasintered material. The crystal structure and properties of thebeta-alumina sintered material are shown in Table 2.

For comparison, beta-alumina sintered materials (sample Nos. 1-3 ofComparative Example 1) were obtained under the same conditions as inExample 1 except that the mixture of raw materials was calcined at1,250° C. for 120 minutes and then ground. Further, beta-aluminasintered materials (sample Nos. 4-6 of Comparative Example 1) wereobtained under the same conditions as in Example 1 except that nomagnesium-aluminum spinel was used. The crystal structures andproperties of these beta-alumina sintered materials (sample Nos. 1-6 ofComparative Example 1) are shown in Table 2.

In Table 2, electrical resistance and strength to internal waterpressure were measured as follows.

Test method for electrical resistance

Electrical resistance was obtained as a value at 350° C. using an Na/Naconductivity tester shown in FIG. 3. In FIG. 3, the Na/Na conductivitytester was constituted by a tubular beta-alumina sintered material (abeta-alumina tube) 1, insulating supports 2 and 3, a stainless steelelectrode 4 and electrode terminals 5 and 6. By feeding molten sodium 8of 350° C. into a container 7 and the beta-alumina tube 1 and passing agiven electricity between the terminals 5 and 6, the electricalresistance of the beta-alumina tube to be measured was determined as aspecific resistance.

Test method for burst strength to internal pressure

A water pressure was applied to the inner wall of a tubular beta-aluminasintered material (a beta-alumina tube) via a rubber tube. The burststrength with respect to internal pressure of the tube was determinedfrom (i) the water pressure when the beta-alumina tube broke and (ii)the dimension of the tube.

                                      TABLE 2                                     __________________________________________________________________________                                         Electrical                                                                          Burst strength                     Sample                          Density                                                                            regisstance                                                                         to internal                        No.       Production conditions and raw materials                                                             (g/cm.sup.3)                                                                       (Ωcm)                                                                         pressure (MPa)                     __________________________________________________________________________                    Molar ratio*.sup.1                                                                    D50*.sup.2                                                                        D90*.sup.3                                        Example 1                                                                           1   Spinel                                                                            A 0.8     1.0 5.0 3.20 3.5   180                                      2       B 1.0     1.0 5.0 3.22 3.4   180                                      3       C 1.1     1.0 5.0 3.23 3.4   180                                      4       D 1.2     1.0 5.0 3.23 3.4   190                                      5       E 1.4     1.0 5.0 3.22 3.5   190                                      6       F 1.5     1.0 5.0 3.20 3.5   180                                      7   Spinel                                                                            G 1.1     0.5 1.0 3.25 3.1   190                                      8       H 1.1     0.5 2.0 3.25 3.1   200                                      9       I 1.1     0.8 4.0 3.23 3.3   190                                      3       C 1.1     1.0 5.0 3.23 3.4   180                                      10      J 1.1     1.0 8.0 3.22 3.4   180                                      11      K 1.1     5.0 10.0                                                                              3.20 3.5   180                                      12      L 1.1     5.0 15.0                                                                              3.20 3.6   180                                Compara-                                                                            1   Calcination conducted. Beta-Alumina                                 tive      particle diameter                                                                           1.0 μm                                                                             3.23 4.5   160                                Example 1                                                                           2                 2.0 μm                                                                             3.21 5.0   120                                      3                 3.0 μm                                                                             3.15 6.4   100                                      4   No spinel used        3.05 6.2   140                                      5   No spinel used                                                                              MgO added.                                                                            3.10 4.8   130                                      6   No spinel used                                                                              MgCO.sub.3 added.                                                                     3.08 5.5   120                                __________________________________________________________________________                                      Average                                                                            Proportion                                                                          Maximum                                                  Degree    particle                                                                           of particles                                                                        particle                                             Sample                                                                            of    Aspect                                                                            diameter                                                                           of 5 μm or                                                                       diameter                                             No. orientation                                                                         ratio                                                                             (μm)                                                                            less (%)                                                                            (μm)                          __________________________________________________________________________                  Example 1                                                                           1   0.35  2.4 1.8  95    120                                                  2   0.34  2.5 1.8  96    130                                                  3   0.34  2.3 1.9  96    150                                                  4   0.35  2.2 1.7  95    120                                                  5   0.33  2.4 1.6  96    130                                                  6   0.35  2.3 1.5  95    100                                                  7   0.24  1.6 2.3  98    90                                                   8   0.27  1.8 2.3  97    80                                                   9   0.31  2.0 2.1  97    100                                                  3   0.34  2.3 1.9  96    150                                                  10  0.34  2.5 2.2  94    120                                                  11  0.37  2.7 2.5  91    160                                                  12  0.38  2.8 2.8  92    180                                            Compara-                                                                            1   0.38  4.2 3.5  87    180                                            tive  2   0.43  4.5 4.2  62    350                                            Example 1                                                                           3   0.48  4.5 5.3  45    400                                                  4                                                                             5                                                                             6                                                         __________________________________________________________________________     *.sup.1 : Spinel composition (MgO/Al.sub.2 O.sub.3 moler ratio)               *.sup.2 : Average particle diameter (μm)                                   *.sup.3 : 90% Particle diameter (μm)                                  

EXAMPLE 2

In order to confirm the effect of addition of sodium compound,beta-alumina sintered materials were obtained under the same steps andconditions as in Example 1 except that various sodium compounds as shownin Table 3 were used. The crystal structures and properties of thebeta-alumina sintered materials obtained are shown in Table 3.

                                      TABLE 3                                     __________________________________________________________________________           Sample                                                                        No.  Kids of spinel and sodium compound(s)                             __________________________________________________________________________    Example 2                                                                            3    Spinel = C                                                                           Na.sub.2 CO.sub.3                                                 13   C      NaHCO.sub.3 /Na.sub.2 CO.sub.3 (molar ratio: 20/80)               14   C      NaHCO.sub.3 /Na.sub.2 CO.sub.3 (molar ratio: 40/60)               15   C      NaHCO.sub.3 /Na.sub.2 CO.sub.3 (molar ratio: 60/40)               16   C      NaHCO.sub.3 /Na.sub.2 CO.sub.3 (molar ratio: 80/20)               17   C      NaHCO.sub.3                                                       18   C      Sodium oxalate                                             __________________________________________________________________________                   Electrical                                                                          Burst strength                                                                        Degree                                                 Sample                                                                            Density                                                                            resistance                                                                          to internal                                                                           of    Aspect                                           No. (g/cm.sup.3)                                                                       (Ωcm)                                                                         pressure (MPa)                                                                        orientation                                                                         ratio                                      __________________________________________________________________________    Example 2                                                                           3   3.23 3.4   180     0.34  2.3                                              13  3.25 3.1   220     0.33  2.0                                              14  3.24 3.1   230     0.33  2.0                                              15  3.25 3.0   220     0.32  2.2                                              16  3.24 3.1   210     0.34  2.1                                              17  3.24 3.2   200     0.33  2.3                                              18  3.24 3.1   210     0.35  2.4                                        __________________________________________________________________________                       Preparation of                                                   Sample                                                                            Average particle                                                                       particles of                                                                            Maximum particle                                       No. diameter (μm)                                                                       5 μm or less (%)                                                                     diameter (μm)                                 __________________________________________________________________________    Example 2                                                                           3   1.9      96        150                                                    13  2.2      94        90                                                     14  2.1      95        80                                                     15  2.3      92        100                                                    16  2.4      93        90                                                     17  2.0      92        110                                                    18  2.1      92        150                                              __________________________________________________________________________

EXAMPLE 3

In order to confirm the effect of alumina material, beta-aluminasintered materials were obtained under the same steps and conditions asin Example 1 except that the average particle diameter and BET specificsurface area of α-Al₂ O₃ material were varied as shown in Table 4. Thecrystal structures and properties of the beta-alumina sintered materialsobtained are shown in Table 4.

                                      TABLE 4                                     __________________________________________________________________________           Sample                                                                             Kids of spinel and material alumina                                      No.                 D50*.sup.1                                                                          BET*.sup.2                                   __________________________________________________________________________    Example 3                                                                            3    Spinel = C                                                                           Alumina = A                                                                           1.5   3.5                                                 19   C      B       0.5   15.5                                                20   C      C       0.5   10.0                                                21   C      D       0.8   10.0                                                22   C      E       0.8   5.0                                                 23   C      F       1.0   5.0                                                 24   C      G       2.0   3.0                                          __________________________________________________________________________                   Electrical                                                                          Burst strength                                                                        Degree                                                 Sample                                                                            Density                                                                            resistance                                                                          to internal                                                                           of    Aspect                                           No. (g/cm.sup.3)                                                                       (Ωcm)                                                                         pressure (MPa)                                                                        orientation                                                                         ratio                                      __________________________________________________________________________    Example 3                                                                           3   3.23 3.4   180     0.34  2.3                                              19  3.25 3.1   190     0.23  1.5                                              20  3.24 3.2   200     0.23  1.4                                              21  3.24 3.2   180     0.25  1.7                                              22  3.24 3.2   180     0.24  1.9                                              23  3.24 3.2   170     0.31  2.0                                              24  3.20 3.4   170     0.37  2.6                                        __________________________________________________________________________                       Preparation of                                                   Sample                                                                            Average particle                                                                       particles of                                                                            Maximum particle                                       No. diameter (μm)                                                                       5 μm or less (%)                                                                     diameter (μm)                                 __________________________________________________________________________    Example 3                                                                           3   1.9      96        150                                                    19  2.2      97        80                                                     20  2.1      98        70                                                     21  2.3      96        100                                                    22  2.1      95        90                                                     23  2.1      95        110                                                    24  2.8      91        150                                              __________________________________________________________________________     *.sup.1 : Average particle diameter (μm)                                   *.sup.2 : Specific surface area (m.sup.2 /g) as measured by BET adsorptio     method.                                                                  

Table 4

In order to confirm the effect of firing conditions, beta-aluminasintered materials were obtained under the same steps and conditions asin Example 1 except that the heat curve for firing was varied as shownin Table 5. The crystal structures and properties of the beta-aluminasintered materials obtained are shown in Table 5.

                                      TABLE 5                                     __________________________________________________________________________    Sample    Heat curve for firing                                                     No. 1st step 2nd step (max. temp.)                                                                    3rd steps                                       __________________________________________________________________________    Example 4                                                                           3   --       1,600° C. × 0.5 hr                                  25  1,450° C. × 1 hr                                                          1,600° C. × 0.5 hr                                                          1,450° C. × 1 hr                         26  1,500° C. × 1 hr                                                          1,600° C. × 0.5 hr                                                          1,500° C. × 1                      __________________________________________________________________________                                  hr                                                             Electrical                                                                          Burst strength                                                                        Degree                                                 Sample                                                                            Density                                                                            resistance                                                                          to internal                                                                           of    Aspect                                           No. (g/cm.sup.3)                                                                       (Ωcm)                                                                         pressure (MPa)                                                                        orientation                                                                         ratio                                      __________________________________________________________________________    Example 4                                                                           3   3.23 3.4   180     0.34  2.3                                              25  3.25 3.0   220     0.33  2.0                                              26  3.24 3.1   210     0.34  2.1                                        __________________________________________________________________________                       Preparation of                                                   Sample                                                                            Average particle                                                                       particles of                                                                            Maximum particle                                       No. diameter (μm)                                                                       5 μm or less (%)                                                                     diameter (μm)                                 __________________________________________________________________________    Example 4                                                                           3   1.9      96        150                                                    25  2.3      97        60                                                     26  2.2      97        80                                               __________________________________________________________________________

As is clear from the above, the beta-alumina sintered materials producedin the scope of the present invention have good properties in electricalresistance, strength to internal water pressure, and the like, and thebeta-alumina sintered materials produced under more preferableconditions have better properties in electrical resistance, strength tointernal water pressure, and the like.

As described above, in the present invention, since the magnesium sourcematerial is fed in the form of magnesium-aluminum spinel, a beta-aluminasolid electrolyte can efficiently be produced without subjecting rawmaterials to calcination.

Further, the beta-alumina solid electrolyte obtained by the presentprocess, having a unique crystal structure in that the beta-aluminacrystals constituting the solid electrolyte have small orientation and asmall aspect ratio, has a low electrical resistance and a high strengthto internal water pressure and is excellent as a diaphragm for asodium-sulfur battery.

What is claimed is:
 1. A beta-alumina solid electrolyte for use in asodium-sulfur battery, wherein the beta-alumina crystals constitutingsaid electrolyte have a degree of orientation toward the C axis thereof,of 0.2-0.4 and an aspect ratio of 4.0 or less.
 2. A beta-alumina solidelectrolyte for use in a sodium-sulfur battery, wherein the beta-aluminacrystals constituting said electrolyte have a degree of orientationtoward the C axis thereof, of 0.2-0.4 and has such a particle diameterdistribution that the average particle diameter is 3 μm or less, theproportion of the particles having a particle diameter of 5 μm or lessis 90% or more, and the maximum particle diameter is 300 μm or less. 3.A beta-alumina solid electrolyte according to claim 1, wherein saidsolid electrolyte has an electrical resistance of 4.0 Ω.cm or less, aburst strength to internal pressure of 150 MPa or more, and a density of3.20 g/cm² or more.
 4. A beta-alumina solid electrolyte according toclaim 2, wherein said solid electrolyte has an electrical resistance of4.0 Ω.cm or less, a burst strength to internal pressure of 150 MPa ormore, and a density of 3.20 g/cm² or more.